Fabrication of Enclosed Nanochannels Using Silica Nanoparticles

ABSTRACT

In accordance with the invention, there is a method of forming a nanochannel including depositing a photosensitive film stack over a substrate and forming a pattern on the film stack using interferometric lithography. The method can further include depositing a plurality of silica nanoparticles to form a structure over the pattern and removing the pattern while retaining the structure formed by the plurality of silica nanoparticles, wherein the structure comprises an enclosed nanochannel.

CROSS REFERENCE TO RELATED APPLICATION

This application is a continuation-in-part application of U.S. patentSer. No. 12/892,427 filed on Sep. 28, 2010, which is a divisionalapplication of U.S. patent application Ser. No. 11/549,732 filed on Oct.16, 2006, which claims priority to U.S. Provisional Patent ApplicationSer. No. 60/726,651 filed on Oct. 17, 2005, the disclosure of which isincorporated by reference herein in its entirety.

GOVERNMENT INTEREST

This invention was made with U.S. Government support under Grant No.DAAD19-99-1-0196 awarded by the Army Research Office and Grant No.HR0011-05-1-0006 awarded by the DOD/Defense Advanced Research ProjectsAgency. The U.S. Government has certain rights in the invention.

FIELD OF THE INVENTION

The subject matter of this invention relates to fabrication ofmicro/nano structures. More particularly, the subject matter of thisinvention relates to nanochannels and a method for fabricating enclosednanochannels using lithography and self assembly of silicananoparticles.

BACKGROUND OF THE INVENTION

Micro and nano structures including nanoparticle assembly with two andthree dimensional periodicity can have potential applications in theareas of photonic crystals, chemical sensors, catalysts, andbiotechnology. Patterned surfaces can be used as hard templates toassist the self assembly of not only relatively simple clusters but alsocomplex and unique crystallization structures. Soft polymer templateshave been used for directed self assembly of particle arrays on flatsubstrates. Binary colloidal crystals have been fabricated using twodifferent sizes of colloidal particles. Further, micro and nanoparticles have been used as templates for the preparation of porousmetallic nanostructures and monodisperse colloidal crystals. Even thoughnanochannel structures for nanofluidic applications have been fabricatedusing thermal oxidation or nanoimprint, there is a need for a simple andinexpensive approach for the fabrication of enclosed channels formed ofnanoparticles.

Thus, there is need to solve these and other problems of the prior artand provide a simple method for the fabrication of nanochannelstructures.

SUMMARY OF THE INVENTION

In accordance with the teachings of the present invention, there is amethod of forming a nanochannel including depositing a photosensitivefilm stack over a substrate and forming a pattern on the film stackusing interferometric lithography. The method can further includedepositing a plurality of silica nanoparticles to form a structure overthe pattern and removing the pattern while retaining the structureformed by the plurality of silica nanoparticles, wherein the structureincludes an enclosed nanochannel.

According to various embodiments, there is a method of forming amultilayer silica nanochannel structure including forming a first layerof silica nanochannels. The step of forming the first layer of silicananochannels having a first spatial period and a first aspect ratioincludes: (a) depositing a film stack over a substrate; (b) forming apattern on the film stack using lithography; (c) depositing a pluralityof silica nanoparticles to form a structure over the pattern; and (d)removing the pattern while retaining the structure formed by theplurality of silica nanoparticles, wherein the structure comprisesenclosed silica nanochannels. The method of forming multilayer silicananochannel can also include forming a second layer of silicananochannel having a second spatial period and a second aspect ratioover the first layer of silica nanochannels by repeating steps a-d toform the second layer of silica nanochannels and repeating steps a-d m−2times to form an m layered silica nanochannel structure.

According to various embodiments, there is another method of forming amultilayer silica nanochannel structure including forming a first layerof silica nanochannels having a first spatial period and a first aspectratio. The step of forming first layer of silica nanochannels includes(a) depositing a film stack over a substrate; (b) forming a pattern onthe film stack using lithography; (c) depositing a plurality of silicananoparticles to form a structure over the pattern. The method offorming a multilayer silica nanochannel structure can further includerepeating the steps a-c to form a second layer of structure having asecond spatial period and a second aspect ratio over the first layer ofstructure. The method can further include repeating the steps a-c (m−2)times to get m layers of structure over m layers of pattern and removingthe m layers of pattern while retaining the structure formed by theplurality of silica nanoparticles, thereby forming m layers of silicananochannel structure.

According to various embodiments there is a nanochannel device forselectively separating components of a fluid including at least onefirst nanochannel having a first opening, at least one secondnanochannel with a second opening, wherein the first opening is in adirection different from the first opening, and at least one poroussidewall having a plurality of pores between the first and the secondnanochannel, wherein the first nanochannel, the second nanochannel, andthe at least one porous sidewall are disposed such that the fluid entersthrough the first opening of the first nanaochannel, percolates throughthe plurality of pores of the porous sidewall and exits through thesecond opening of the second nanochannel.

According to various embodiments, there is a method of diagnosingnanochannel formation. The method can include depositing a drop of asuspension including silica nanoparticles on a patterned surface,determining that a nanochannel is not completely formed if thesuspension of silica nanoparticles forms an elongated drop along adirection of the pattern, and determining that a top of the nanochannelis formed if the suspension of silica nanoparticles shows wetting.

In implementations, a method of forming a nanochannel is disclosed. Themethod can include depositing a photosensitive film stack over asubstrate; forming a first pattern on the film stack usinginterferometric lithography to form a nanochannel; forming a secondpattern on the film stack using interferometric lithography and a maskaligner to form a barrier in the nanochannel; depositing a plurality ofsilica nanoparticles to form a structure over the pattern; and removingthe first pattern and the second pattern while retaining the structureformed by the plurality of silica nanoparticles, wherein the structurecomprises an enclosed nanochannel with the barrier formed along aportion of the enclosed nanochannel.

In implementations, the depositing a photosensitive film stack cancomprise depositing a first layer comprising an antireflective coatingover the substrate and depositing a second layer comprising aphotoresist over the first layer.

In implementations, the second layer can comprise a layer of positivephotoresist or a layer of negative photoresist.

In implementations, the depositing the plurality of silica nanoparticlescan comprise at least one cycle of spin coating using a suspension ofsilica nanoparticles.

In implementations, the depositing the plurality of silica nanoparticlescan comprise multiple cycles of spin coating wherein each cycle of spincoating uses a suspension of silica nanoparticles with a same sizedistribution.

In implementations, the depositing the plurality of silica nanoparticlescan comprise multiple cycles of spin coating wherein at least one cycleof spin coating uses a suspension of silica nanoparticles with a sizedistribution different than the other cycles of spin coating.

In implementations, a nanochannel device for selectively separatingcomponents of a fluid is disclosed. The nanochannel device can compriseat least one first nanochannel comprising a first opening, a secondopening, and a barrier positioned between the first opening and thesecond opening, wherein the barrier comprises a plurality of pores toallow fluid to flow from the first opening to the second opening.

In implementations, the nanochannel device can further comprise a secondnanochannel arranged perpendicular to the first nanochannel andseparated from the first nanochannel by a barrier comprised of aplurality of pores to allow fluid to flow from the first nanochannel tothe second nanochannel.

In implementations, the second nanochannel can comprise a first opening,a second opening, and a barrier positioned between the first opening andthe second opening, wherein the barrier comprising a plurality of poresto allow fluid to flow from the first opening to the second openingwherein a thickness and/or a pore size, controlled by the nanoparticlesize, of the barrier between the first opening and the second opening isadjusted relative to the thickness and or the pore size, controlled bythe nanoparticle size, of the barrier between the first and the secondnanochannel to affect the flow of moieties across the two barriers.

In implementations, the nanochannel device can comprise at least oneporous divider arranged between the first and the second nanochannel.

In implementations, the at least one porous divider can comprise aplurality of pores between the first and the second nanochannel, whereinthe first nanochannel, the second nanochannel, and the at least oneporous divider are disposed such that the fluid enters through the firstopening of the first nanochannel, percolates through the plurality ofpores of the porous divider and exits through the second opening of thesecond nanochannel.

In implementations, the nanochannel device can further comprisefunctionalized silica nanoparticles to selectively transport onecomponent of the fluid.

In implementations, the nanochannel device can further comprise a CVDfilm providing sealing of the top surface of the roof of thenanochannels.

In implementations, the CVD film can be composed of SiO₂ and Si3N4.

In implementations, the nanochannel device can further comprise anatomic layer deposited film atop the chemical vapor deposited film,where the atomic layer deposited film can be Al₂O₃.

Additional advantages of the embodiments will be set forth in part inthe description which follows, and in part will be obvious from thedescription, or may be learned by practice of the invention. Theadvantages will be realized and attained by means of the elements andcombinations particularly pointed out in the appended claims.

It is to be understood that both the foregoing general description andthe following detailed description are exemplary and explanatory onlyand are not restrictive of the invention, as claimed.

The accompanying drawings, which are incorporated in and constitute apart of this specification, illustrate embodiments of the invention andtogether with the description, serve to explain the principles of theinvention.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1A to 1E illustrate an exemplary method of forming nanochannelsusing silica nanoparticles in accordance with various embodiments of thepresent teachings.

FIGS. 1F and 1G illustrate another embodiment of an exemplary method offorming nanochannels using silica nanoparticles.

FIGS. 2A-2C illustrates exemplary methods of making multilayer structureof silica nanoparticles.

FIG. 3 is a schematic illustration of an exemplary perpendicular layerednanochannel structure.

FIG. 4 illustrates another exemplary multilayer nanochannel structureaccording to various embodiments of the present teachings.

FIG. 5 depicts an exemplary nanochannel device for selectivelyseparating components of a fluid in accordance with the presentteachings.

FIGS. 6A and 6B depict another exemplary nanochannel device forselectively separating components of a fluid in accordance with thepresent teachings.

FIGS. 7A to 7F depict another exemplary nanochannel device 700 forselectively separating components of a fluid in accordance with thepresent teachings.

FIG. 8 illustrates an exemplary method of forming nanochannels usingsilica nanoparticles in accordance with various embodiments of thepresent teachings.

DESCRIPTION OF THE EMBODIMENTS

Reference will now be made in detail to the present embodiments,examples of which are illustrated in the accompanying drawings. Whereverpossible, the same reference numbers will be used throughout thedrawings to refer to the same or like parts.

Notwithstanding that the numerical ranges and parameters setting forththe broad scope of the invention are approximations, the numericalvalues set forth in the specific examples are reported as precisely aspossible. Any numerical value, however, inherently contains certainerrors necessarily resulting from the standard deviation found in theirrespective testing measurements. Moreover, all ranges disclosed hereinare to be understood to encompass any and all sub-ranges subsumedtherein. For example, a range of “less than 10” can include any and allsub-ranges between (and including) the minimum value of zero and themaximum value of 10, that is, any and all sub-ranges having a minimumvalue of equal to or greater than zero and a maximum value of equal toor less than 10, e.g., 1 to 5. In certain cases, the numerical values asstated for the parameter can take on negative values. In this case, theexample value of range stated as “less that 10” can assume negativevalues, e.g. −1, −2, −3, −10, −20, −30, etc.

FIGS. 1A-1E depict an exemplary method for fabricating a nanochannel 160using interferometric lithography and standard semiconductor processingtechniques, such as, for example, spin-coating in accordance withvarious embodiments of the present teachings. There are severaladvantages for using semiconductor processing, such as, scalability tolarge area and multilevel processing and integration of nanochannelswith other nano/micro/macro components including fluidic, electronic,mechanical, MEMS (micro electromechanical), and optical subsystems orcomponents. The enclosed silica nanochannels fabricated using standardsemiconductor processing and interferometric lithography can bepotentially useful in photonics, sensory, biological separation,bio-mimic structure, nanofluidics, and catalytic applications.

As shown in FIG. 1A, the method of forming a nanochannel 160 can includedepositing a photosensitive film stack 120 over a substrate 110.Non-limiting examples of the substrate 110 can include a pre-cleanedsilicon wafer, quartz, and sapphire. In some embodiments, depositing thefilm stack 120 can include depositing a first layer 125 including anantireflective coating over the substrate 110 and depositing a secondlayer 126 including a photoresist over the first layer 125. Inaccordance with various embodiments, the first layer 125 can include abottom anti-reflective coating (BARC) for i-line photoresist. Yet inother embodiments, the first layer 125 can include a g-line BARC or adeep UV BARC. Non limiting examples of BARC can be XHRiC-16 and Wet-i™10-7, manufactured by Brewer Science, Inc. (Rolla, Mo.). In variousembodiments, the first layer 125 can be deposited using standard spincoating procedure. In other embodiments, the deposition of the firstlayer 125 can also include baking the first layer 125 at a temperaturefrom about 100° C. to about 250° C. for about 60 second to about 120second. The second layer 126 can include at least one of a layer ofpositive photoresist and a layer of negative photoresist. In certainembodiments, the photoresist can be an i-line photoresist. In otherembodiments, the photoresist can be a g-line or a deep UV photoresist. Anon limiting exemplary positive photoresist can be SPR510A manufacturedby Shipley/Rohm & Haas Electronic Materials (Marlborough, Mass.), and anon limiting exemplary negative photoresist can be NR7-500P,manufactured by Futurrex, Inc. (Franklin, N.J.). The deposition of thesecond layer 126 including photoresist can also include a baking step toremove residual solvent. In various embodiments, the first layer 125 canhave a thickness from about 50 nm to about 200 nm and the second layer126 can have a thickness from about 200 nm to about 1500 nm.

Referring to FIG. 1B, the method of forming a nanochannel 160 can alsoinclude forming a pattern 130 on the film stack 120 using lithography.In some embodiments, the pattern 130 can be formed using interferometriclithography. In interferometric lithography, two coherent laser beamswith wavelength λ are intersected at an angle 2θ to produce a periodicinterference pattern on the film stack 120 with a spatial period d=λ/(2sin θ). The angle between the two laser beams can determine the patternspatial period while the exposure, time, power density, and developmenttime can determine the line width and the pattern morphology. Accordingto various embodiments, a laser in the UV range consistent with thephotosensitivity of the film stack 120 can be used to form the periodicinterference pattern 130 on the film stack 120, for example, a 248 nmlaser can be used for deep UV photoresist and a 355 nm laser can be usedfor i-line photoresist. Non-limiting examples of a laser in the UV rangecan include a 355 nm tripled yttrium-aluminum-garnet (YAG) laser, a 248nm KrF excimer laser, a 193 nm ArF excimer laser, and a 157 nm F₂excimer laser. In various embodiments, using a 355 nm laser, one canform a pattern 130 on the film stack 120 with a spatial period greaterthan about 200 nm. In other embodiments, an ArF laser can be used toform a pattern 130 on the film stack 120 with a spatial period as smallas about 68 nm and with frequency doubling as small as about 34 nm. Insome embodiments, the method of forming a pattern 130 on the film stack120 can include immersion interference lithography. Immersioninterference lithography can extend the spatial period of the pattern130 to λ/2n, where n is the immersion liquid refractive index. In otherembodiments, the method of forming the pattern 130 on the film stack 120can include conventional lithography either in the ultra-violet (UV) ordeep UV region. The step of forming a pattern 130 on the film stack 120can further include a bake and develop cycle. In some embodiments, thestep of forming a pattern 130 on the film stack 120 can further includeetching the first layer 125 including an antireflective coating.

As shown in FIGS. 1C and 1D, the method of forming a nanochannel 160 caninclude depositing a plurality of silica nanoparticles 140 to form astructure 150 over the pattern 130. In some embodiments, silicananoparticles 140 can be deposited by spin coating a colloidaldispersion of silica nanoparticles. In other embodiments, silicananoparticles 140 can be deposited over the pattern 130 usingalternative deposition techniques such as, but not limited to, dipcoating, convective deposition, and layer by layer electrostaticdeposition. In various embodiments, the step of depositing silicananoparticles 140 can include at least one cycle of spin coating using asuspension of silica nanoparticles. In some embodiments, the step ofdepositing a plurality of silica nanoparticles 140 can include multiplecycles of spin coating wherein each cycle of spin coating uses asuspension of silica nanoparticles with a same size distribution. Inother embodiments, the step of depositing a plurality of silicananoparticles 140 can include multiple cycles of spin coating wherein atleast one cycle of spin coating uses a suspension of silicananoparticles with a size distribution different than the other cyclesof spin coating. While not intending to be bound by any specific theory,it is believed that various cycles of spin coating utilizing suspensionsof silica nanoparticles with different size distributions can fill thespaces between the walls of the pattern 130 on the film stack 120 andcan also control the thickness of the top sealing layer. For example, insome embodiments, colloidal solutions or suspensions of three differentsize distributions of silica nanoparticles can be used in threedifferent cycles of spin coating to form the structure 150 over thepattern 130. Exemplary colloidal solutions of silica nanoparticles caninclude Snowtex® series of colloidal silica: ST-C with a particle sizein the range of about 10 nm to about 20 nm, ST-OL with a particle sizein the range of about 40 nm to about 50 nm, and ST-ZL with a particlesize in the range of about 70 nm to about 100 nm, manufactured by NissanChemical America Corporation (Houston, Tex.). The colloidal solutions ofsilica nanoparticles can be diluted with deionized water to get thedesired concentration for spin coating. In some embodiments, colloidalsilica nanoparticles can be used in the concentration range of about 1wt. % to about 10 wt. and in some cases from about 4 wt. % to about 6wt. %. In various embodiments, the method of forming a nanochannel 160can also include agitating the colloidal solution of silicananoparticles in an ultrasonic bath before spin coating. In someembodiments, the cycle of spin coating can include baking to remove anyresidual solvent, for example such as baking at a temperature from about60° C. to about 120° C. for about 1 minute to about 8 minutes.

As shown in FIG. 1E, the method of forming a nanochannel 160 can includeremoving the pattern 130 while retaining the structure 150 formed by theplurality of silica nanoparticles 140. According to various embodiments,removing the pattern 130 can be achieved by calcination. Calcination canbe carried out by heating a substance to a high temperature, but belowits melting point in the presence of air or controlled environment tobring about thermal decomposition or phase transition in its chemical orphysical structure. In some embodiments, the calcination can be carriedat about 700° C. to about 900° C. for about 1 hour to about 3 hours andin some cases at about 800° C. for about 1.5 to about 2 hours. Invarious embodiments, the high temperature calcination can induce somedegree of sintering between the silica nanoparticles 140 and therebyenhancing the mechanical stability of the nanochannel structure 150. Inother embodiments, the pattern 130 can be removed by techniques such as,but not limited to chemical, plasma, and reactive ion etching. Yet insome other embodiments, piranha composition such 1:1, 1:1.5, and 1:2::30% H₂O₂: 98% H₂SO₄ can be used either alone or in combination withcalcination to remove the pattern 130, while retaining the silicananoparticle structure 150.

According to various embodiments, the method of forming a nanochannel160 can further include depositing a plurality of silica nanoparticles140 over the substrate 110 before the step of depositing aphotosensitive film stack 120 over the substrate 110, as shown in FIG.1F.

According to various embodiments, the method of forming a silicananochannel 160 can further include at least one of increasing theconcentration of suspension, adding some bonding agents and increasingthe humidity during spin coating to slow the drying process to preventcracking in the sealing layer. In some embodiments, a bonding agent suchas, but not limited to polyvinylpyrrolidone (PVP) can be added to theaqueous colloidal solution of silica and ethylene glycol can be added tothe ethanol colloidal solution of silica to prevent cracking in thesealing layer.

In various embodiments, the method of forming a nanochannel 160 can alsoinclude modifying the surface of silica nanoparticles 140 to provideadditional functionality. In some embodiments, the surface of silicananoparticles 140 can be modified to provide additional functionalitybefore the step of depositing a plurality of silica nanoparticles 140 toform a structure 150 over the pattern 130, wherein the step of removingthe pattern 130 is compatible with the functionalization. In otherembodiments, the surface of silica nanoparticles 140 can be modifiedafter the step of removing the pattern 130 while retaining the structure150 formed by the plurality of silica nanoparticles 140. In someembodiments, the surface of silica nanoparticles can be functionalizedto bind biologically active molecules for optical and/or electricalanalysis. In other embodiments, a thin layer of gold or silver can bedeposited on silica nanoparticles to increase sensitivity of the silicananoparticles to biomolecules. In various embodiments, the surface ofsilica nanoparticles can be functionalized for one or more of photonics,catalysis, chemical/biological sensing, separation, bio-mimic structure,and nanofluidic applications. Furthermore, according to variousembodiments, there is a device formed by the exemplary method as shownin FIGS. 1A to 1E including a nanochannel structure, wherein thenanochannel structure includes silica nanoparticles 140 having afunctionalized surface for one or more of photonics, catalysis,chemical/biological sensing, separation, bio-mimic structure, andnanofluidic applications.

According to various embodiments, the method of forming a nanochannel160 can further include depositing a releasing layer 112 includingchromium over the substrate 110 and under the silica nanoparticles 140,and immersing the structure 150 of silica nanoparticles 140 includingnanochannels 160 in a boiling aqueous sulfuric acid solution, therebyreleasing the free-standing structure 150 of silica nanoparticles 140including nanochannels 160. In some embodiments, a support layer 114 toprovide mechanical support to the nanochannels 160 can be deposited overthe releasing layer 112 as shown in FIG. 1G. In various embodiments, thesupport layer 114 can comprise silicon nitride. In some otherembodiments, the method of forming a nanochannel 160 can further includedepositing a support layer 114 over the substrate 110 and under thesilica nanoparticles 140, and selectively etching the substrate 110,thereby releasing the free-standing structure 150 of silicananoparticles 140 including nanochannels 160 on the support layer 114.

According to various embodiments, there is a method of diagnosing thestage of the nanochannel 160 formation. The method can includedepositing a drop of a suspension including silica nanoparticles on apatterned surface. The method can also include determining that ananochannel 160 is not completely formed if the suspension of silicananoparticles forms an elongated drop along a direction of the pattern130 due to hydrophobic surface of the silicon substrate 110 andphotoresist 125 of pattern 130 and determining that a top of thenanochannel is formed if the suspension of silica nanoparticles showswetting due to hydrophilic surface of silica nanoparticles 140. Forexample, upon application of one or more drops of a suspension on thepattern 130 shown in FIGS. 1B and 1C, but before spinning, thesuspension of silica nanoparticles can form an elongated drop along thedirection of the pattern 130 due to the hydrophobic surface propertiesof the substrate 110 and the photoresist 126. Once the channel tops areformed as shown in FIG. 1D, partial wetting of the drop of suspension ofsilica nanoparticles can be observed due to the hydrophilicity of thesilica nanoparticles and no contact of the one or more drops of asuspension of silica nanoparticles with the hydrophobic photoresist 126.

According to various embodiments, there is a method of forming amultilayer silica nanochannel structure 200 as shown in FIGS. 2A and 2C.The method of forming a multilayer silica nanochannel structure 200 caninclude forming a first layer 262 of silica nanochannels 260 having afirst spatial period and a first aspect ratio. The term “aspect ratio”used herein refers to a ratio of height to width of the silicananochannels 260. In various embodiments, the method of forming thefirst layer 262 of silica nanochannels 260 can include: (a) depositing afilm stack 120 over a substrate 110; (b) forming a pattern 130 on thefilm stack 120 using lithography; (c) depositing a plurality of silicananoparticles 140 to form a structure 150 over the pattern; and (d)removing the pattern 130 while retaining the structure 150 formed by theplurality of silica nanoparticles 140. The structure 150 can includeenclosed silica nanochannels 160, as depicted in FIGS. 1E to 1G. Themethod of forming a multilayer silica nanochannel structure 200 canfurther include forming a second layer 264 of silica nanochannels 260′having a second spatial period and a second aspect ratio over the firstlayer 262 of silica nanochannels 260 by repeating the steps a-d employedin forming the first layer 262 of silica nanochannels 260. In variousembodiments, the steps a-d can be repeated m−2 times to form an mlayered silica nanochannel structure 200. In some embodiments, the firstspatial period and the first aspect ratio can be the same as the secondspatial period and second aspect ratio. In other embodiments, the firstspatial period and the first aspect ratio can be different from thesecond spatial period and second aspect ratio.

According to various embodiments, there is another exemplary method offorming a multilayer silica nanochannel structure 200 as shown in FIGS.2B and 2C. The method can include forming a first layer of structure 252having a first spatial period and a first aspect ratio over the pattern230 by (a) depositing a film stack 120 over a substrate 110, (b) forminga pattern 130 on the film stack 120 using lithography, (c) depositing aplurality of silica nanoparticles 140 to form a structure 150, 252 overthe pattern 130, 230. The method can include repeating the steps a-c toform a second layer of structure 254 having a second spatial period anda second aspect ratio over the first layer of structure 252 as shown inFIG. 2B. The method can further include repeating the steps a-c (m−2)times to get m layered structure 200″. The method can further includeremoving the m layers of pattern 230, 230′ while retaining the structure252, 254 formed by the plurality of silica nanoparticles 140, therebyforming m layered silica nanochannel structure 200. In variousembodiments, the first spatial period and the first aspect ratio can besame as the second spatial period and second aspect ratio. In otherembodiments, the first spatial period and the first aspect ratio can bedifferent from the second spatial period and second aspect ratio.

According to various embodiments, the method of forming a multilayersilica nanochannel structure 200 can further include rotating thesubstrate 110 to a desired angle during the formation of a m^(th) layerof silica nanochannels to form the m^(th) layer at the desired anglerelative to the (m−1)^(th) layer. In some embodiments, the layers can beat an angle in the range of about 0° to about 90°. FIG. 3 is a schematicillustration of an exemplary substantially perpendicular layerednanochannel structure 300 wherein a plurality of nanochannels 360 in afirst layer 362 with a first spatial period and first aspect ratio areperpendicular to a plurality of nanochannels 360′ in the second layer364 with a second spatial period and a second aspect ratio. In someembodiments, the first spatial period and the first aspect ratio can besame as the second spatial period and the second aspect ratio. In otherembodiments, the first spatial period and the first aspect ratio can bedifferent from the second spatial period and the second aspect ratio.

FIG. 4 illustrates another exemplary multilayer nanochannel structure400 according to various embodiments of the present teachings. Themultilayer nanochannel structure 400 can include at least one layer 462including at least one enclosed silica nanochannel 460 and at least onelayer 464 including at least one open silica nanochannel 470. In someembodiments, the multilayer silica nanochannel structure can includehybrid enclosed structures such as one dimensional channels and twodimensional cavities in other layers, as disclosed in D. Xia, S. R. J.Brueck, Nano Letters, 2004, Vol. 4, No. 7, 1295, which is incorporatedby reference herein in its entirety.

According to various embodiments, there is porosity between thenanochannels 160 and between different layers 262, 264. The porosity ofthe nanochannel structure 200, 300, 400 can be of the scale of d/3,where d is the diameter of the silica nanoparticles and can becontrolled with the size of the silica nanoparticles. A porous sidewall562 including a plurality of pores 595 between nanochannels 560 and 560′is shown in FIG. 5.

FIG. 5 depicts an exemplary nanochannel device 500 for selectivelyseparating components of a fluid 590. The exemplary nanochannel device500 includes at least one first nanochannel 560 with a first opening 582and at least one second nanochannel 560′ with a second opening 584,wherein the first opening 582 is in a direction different from the firstopening 584. The exemplary nanochannel device 500 can further include atleast one porous sidewall 562 having a plurality of pores 595 betweenthe first 560 and the second 560′ nanochannel, wherein the firstnanochannel 560, the second nanochannel 560′, and the at least oneporous sidewall 562 are disposed such that the fluid 590 enters throughthe first opening 582 opening of the first nanaochannel 560, percolatesthrough the plurality of pores 595 of the porous sidewall 562 and exitsthrough the second opening 584 of the second nanochannel 560′. Invarious embodiments, the silica nanoparticles 540 can be functionalizedto selectively transport one component of the fluid 590.

According to various embodiments, the method of forming silicananochannel 160 and silica nanochannel structure 200 can have numerousdegrees of freedom. In some embodiments, the spatial period, shape, andsize of the nanochannels 160 can be controlled by varying thelithographic parameters such as thickness and photoresist type (i.e.positive or negative photoresist), exposure, development times, anddevelop parameters (such as postbake time and temperature, developerconcentration, temperature and time). In other embodiments, the silicananochannel 160 profile can be controlled by controlling the spincoating process (spin program and the number of deposition cycle),concentration of colloidal silica nanoparticles and silica nanoparticlesize.

FIGS. 6A and 6B depict an exemplary nanochannel device 600, similar tothat depicted in FIG. 5, for selectively separating components of afluid 690. Nanochannel device 600 is shown as a two level chip withcross channels and a porous layer functioning as a separation media,which can function to filter and collect separated molecules. A firstlayer of silica nanochannels 605 is first formed using the processesdescribed above. A second layer of silica nanochannels 610 is thenformed on top of the silica nanoparticles such that the nanochannelarray in the second layer is arranged perpendicular to the nanochannelarray in the first layer. The calcination step to remove the photoresistmaterial can be performed once for each layer, or reserved until bothlayers of nanochannels are formed. For example, each of the nanochannelsin the first and the second layer can be about 500-nm wide. One or moresilica nanoparticle barriers are formed within the second layer ofsilica nanochannels. As shown in FIG. 6A, a silica nanoparticle barrier615 can provide a zone for biological molecules (e.g., DNA) toaccumulate. Controlling the thickness of the roof of the first layer ofnanochannels 605 relative to the width of the barrier or barriers 615provides a means of adjusting the separation processes. The biologicalmolecules can then move through the top channels accumulate along thebarrier and penetrate through the porous roof into the bottom layer andmove in a perpendicular direction. A buffer solution can be added toprovide conductivity. An applied electric field to the wells can driveDNA in the top channels and provide fast accumulation at the barrier.The applied electric field can then be applied between the top andbottom layers of nanochannels to drive molecules across the porous roof.Molecules that penetrate into the first layer can be removed from thechannels by an electric field applied to the pair of wells in the bottomlayer, as shown in FIG. 6B. Controlling the field strength and thelength of time it is applied provides further degrees of freedom inadjusting the separation processes.

FIGS. 7A-7F depict an exemplary nanochannel device 700, similar to thatdepicted in FIG. 5, for selectively separating components of a fluid 790with the difference being that in FIG. 5 the nanochannels are paralleland separated by a long porous barrier. Adjacent nanochannels need to beopened/closed at the two ends with is difficult since the channels canbe closer than typical lithographic resolutions. This is avoided in FIG.7 by having the nanochannels aligned and separated by a narrow barrierregion. Nanochannel device 700 (with one barrier) and 750 (with threebarriers) comprises nanochannels 710 and one or more barriers 705 fromnanoparticles manufactured perpendicular to the channels. The one ormore barriers 705 can be fabricated by additional illumination ofphotoresist patterns after interferometric lithography on a mask alignerbefore development of the photoresist and spinning of the silicananoparticles. The one or more barriers 705 can be relatively thin, forexample, about 3 μm in thickness, limited only by the size of thenanoparticles and the available lithography. However, this is merely oneexample of barrier thickness and other suitable thicknesses can also beused. A chip with a barrier (3 μm) is shown in FIG. 7A, enlarged area ofinterest is shown in FIG. 7B from the top and in FIG. 7C from the side.It is also possible to make several barriers for different types offiltration. A chip with three barriers perpendicular to the channels isshown in FIG. 7D, enlarged area of interest is shown in FIG. 7E from thetop and in FIG. 7F from the side.

For example nanochannel devices 700 and 750 can be fabricated using thetechniques discussed above. In particular, a photosensitive film stackcan be deposited over a substrate. A first pattern can be formed on thefilm stack using interferometric lithography. This film stack isdeveloped and nanoparticles are deposited by spin coating to form anarray of nanochannels. A second pattern can be formed on a second filmstack deposited over the first layer of nanochannels usinginterferometric lithography and a mask aligner to form one or morebarriers in the nanochannel. A plurality of silica nanoparticles can bedeposited to form the second layer of nanochannels which incorporatesthe one or more barriers. Finally, the first pattern and the secondpattern can be removed, for example by heating in an oxygen ambient,while retaining the structure formed by the plurality of silicananoparticles, wherein the structure comprises an enclosed nanochannelwith the one or more barriers formed along a portion of the enclosednanochannels.

Evaporation through the roof of the nanochannels into the ambient abovethe chip limits the duration of an experiment due to drying of thefluid. Additionally, under an applied electric field, the fluid cantransport through the roof instead of the barriers and bead up on thetop surface of the roof. It is desirable to provide a sealant for theroof while still allowing diffusion of the liquid and biologicalmoieties through the porous walls. Since the roof and walls are porous,this requires line-of-sight deposition technique such that thedeposition is self-sealing on the top few layers of the roof and doesnot penetrate into channel regions, leaving the porosity of the barriersand the channel walls. Chemical vapor deposition (CVD) of a film 806over the roof significantly decreases the evaporation through the roof.Both Si₃N₄ and SiO₂ films have been used successfully as shownschematically in FIG. 8. An additional atomic layer deposition (ALD)step 807 following the CVD step provides additional sealing. It isimportant to block the openings into the nanochannel areas during thisALD step to avoid ALD sealing of the barriers and channel walls. Amongother materials, Al₂O₃ can be used for this atomic layer depositionstep.

Following examples set forth below illustrate different degrees offreedom that can be utilized in practicing the present teachings. Itwill be apparent to one of ordinary skill in the art, however, that thepresent teachings can be practiced with many other sets of parameters inaccordance with the disclosure.

Example 1 Preparation of Enclosed Silica Nanochannels

Enclosed silica nanochannels with a height of about 300 nm and a widthof about 120 nm on a about 1 cm long substrate were obtained usingsilica nanoparticles with diameter in the range of about 40 nm to about50 nm. Interferometric lithography with a 355 nm tripledyttrium-aluminum-garnet (YAG) laser was used to produce the periodicpattern. Snowtex® series of colloidal silica, ST-OL was used in sixcycles of spin coating and calcination at about 800° C. was done forabout 2 hours. The thickness of the sealing layer was in the range ofabout 100 nm to about 150 nm (i.e. 2-3 particles).

Example 2 Preparation of High Aspect Ratio Silica Nanochannels

High aspect-ratio silica nanoparticle walls in the range of about 2:1 toabout 4:1 and thin top seals (with one to two silica nanoparticles) wereobtained using a thick coat of negative photoresist (NR7-500P fromFuturrex, Inc.). The thickness of the negative photoresist was in therange of about 500 nm. Silica nanoparticles with a diameter of about 50nm were used to form high aspect ratio nanochannels with a spatialperiod of about 500 nm and about 1000 nm. Silica nanochannels with aspatial period of about 1000 nm were obtained using silica nanoparticleshaving a diameter of about 80 nm. Furthermore. silica nanochannels withspatial period of about 500 nm were obtained with silica nanoparticleshaving a diameter of about 15 nm.

Example 3 Preparation of Two Layered Silica Nanochannel Structures

Two layer silica nanochannel structures were fabricated using silicananoparticles having a diameter of about 50 nm, through repeatprocessing on a single substrate. After a first layer of buried silicananochannels was fabricated, the full process, including application ofantireflective coating and photoresist films, interferometriclithographic pattern definition and development, spin coating of silicananoparticles, and calcination led to formation of a second layer ofenclosed nanochannels over the first layer. In one case, the silicananochannels in the first layer were parallel to the second layer withboth layers having a spatial period of about 500 nm. In another case,the silica nanochannels in the first layer with a spatial period ofabout 1000 nm were perpendicular to the second layer with spatial periodof about 500 nm.

According to various embodiments, there is a device including at leastone of a single layer, multi layer, and a combination of single andmulti layer nanochannel structure, wherein the nanochannel structure caninclude silica nanoparticles with a functionalized surface to bindbiological molecules for optical and/or electrical analysis. In someembodiments, the surface of silica nanoparticles can be functionalizedfor at least one of photonics, catalysis, chemical/biological sensing,separation, bio-mimic structure, and nanofluidic applications.

While the invention has been illustrated with respect to one or moreimplementations, alterations and/or modifications can be made to theillustrated examples without departing from the spirit and scope of theappended claims. In addition, while a particular feature of theinvention may have been disclosed with respect to only one of severalimplementations, such feature may be combined with one or more otherfeatures of the other implementations as may be desired and advantageousfor any given or particular function. Furthermore, to the extent thatthe terms “including”, “includes”, “having”, “has”, “with”, or variantsthereof are used in either the detailed description and the claims, suchterms are intended to be inclusive in a manner similar to the term“comprising.”

Other embodiments of the invention will be apparent to those skilled inthe art from consideration of the specification and practice of theinvention disclosed herein. It is intended that the specification andexamples be considered as exemplary only, with a true scope and spiritof the invention being indicated by the following claims.

What is claimed is:
 1. A method of forming a nanochannel comprising: depositing a photosensitive film stack over a substrate; forming a first pattern on the film stack using interferometric lithography to form a nanochannel; forming a second pattern on the film stack using interferometric lithography and a mask aligner to form a barrier in the nanochannel; depositing a plurality of silica nanoparticles to form a structure over the pattern; and removing the first pattern and the second pattern while retaining the structure formed by the plurality of silica nanoparticles, wherein the structure comprises an enclosed nanochannel with the barrier formed along a portion of the enclosed nanochannel.
 2. The method of claim 1, wherein the depositing a photosensitive film stack comprises depositing a first layer comprising an antireflective coating over the substrate and depositing a second layer comprising a photoresist over the first layer.
 3. The method of claim 2, wherein the second layer comprises a layer of positive photoresist or a layer of negative photoresist.
 4. The method of claim 1, wherein the depositing the plurality of silica nanoparticles comprises at least one cycle of spin coating using a suspension of silica nanoparticles.
 5. The method of claim 1, wherein the depositing the plurality of silica nanoparticles comprises multiple cycles of spin coating wherein each cycle of spin coating uses a suspension of silica nanoparticles with a same size distribution.
 6. The method of claim 1, wherein the depositing the plurality of silica nanoparticles comprises multiple cycles of spin coating wherein at least one cycle of spin coating uses a suspension of silica nanoparticles with a size distribution different than the other cycles of spin coating.
 7. A nanochannel device for selectively separating components of a fluid comprising: at least one first nanochannel comprising a first opening, a second opening, and a barrier positioned between the first opening and the second opening, wherein the barrier comprises a plurality of pores to allow fluid to flow from the first opening to the second opening.
 8. The nanochannel device of claim 7, further comprising a second nanochannel arranged perpendicular to the first nanochannel and separated from the first nanochannel by a barrier comprised of a plurality of pores to allow fluid to flow from the first nanochannel to the second nanochannel.
 9. The nanochannel device of claim 8, wherein the second nanochannel comprises a first opening, a second opening, and a barrier positioned between the first opening and the second opening, wherein the barrier comprising a plurality of pores to allow fluid to flow from the first opening to the second opening wherein a thickness and/or a pore size, controlled by the nanoparticle size, of the barrier between the first opening and the second opening is adjusted relative to the thickness and or the pore size, controlled by the nanoparticle size, of the barrier between the first and the second nanochannel to affect the flow of moieties across the two barriers.
 10. The nanochannel device of claim 7, comprising at least one porous divider arranged between the first and the second nanochannel.
 11. The nanochannel device of claim 10, where the at least one porous divider comprises a plurality of pores between the first and the second nanochannel, wherein the first nanochannel, the second nanochannel, and the at least one porous divider are disposed such that the fluid enters through the first opening of the first nanochannel, percolates through the plurality of pores of the porous divider and exits through the second opening of the second nanochannel.
 12. The nanochannel device of claim 7, further comprising functionalized silica nanoparticles to selectively transport one component of the fluid.
 13. The nanochannel device of claim 7, further comprising a CVD film providing sealing of the top surface of the roof of the nanochannels.
 14. The nanochannel device of claim 8 wherein the CVD film is composed of SiO₂ and Si₃N₄.
 15. The nanochannel device of claim 13, further comprising an atomic layer deposited film atop the chemical vapor deposited film.
 16. The nanochannel device of claim 15 wherein the atomic layer deposited film is Al₂O₃. 